Removal of per- and polyfluoroalkyl substances and organic fluorine from sewage sludge and sea sand by pyrolysis

Abstract

Pyrolysis is one method for treating sewage sludge, particularly in remote areas or decentralised systems. The end product of pyrolysis, sludge-char, can serve as a soil improver. However, there is a lack of comprehensive data on the organic pollutants’ behaviour in sludge-char. In our work, we focused on the behaviour of per- and polyfluoroalkyl substances (PFASs). Sludge was pyrolyzed at 200–700 °C to determine the minimum safe temperature for effective PFASs removal. It is important to note that PFASs may not only be mineralized but also cleaved to unanalyzed PFASs and other organofluorinated substances. To address this issue, we incorporated additional measurements of organic fluorine in the experiment using combustion ion chromatography (CIC). Due to the inherent heterogeneity of sludge, containing a variety of pollutants and their precursors, we conducted pyrolysis on artificially contaminated sand. This allowed us to assess and compare the behaviour of PFASs in a homogeneous matrix. Based on our analyses, we determined that a temperature greater than 400 °C is imperative for effective PFASs and organic fluorine removal. The results were verified by analyzing samples from a commercial sludge pyrolysis unit at the Bohuslavice-Trutnov WWTP, which confirmed our measurements. In light of these results, it becomes evident that sludge pyrolysis below 400 °C is unsuitable for PFAS removal from sewage sludge.

Highlights

•	The minimum temperature for significant PFASs and organic fluorine removal was 400 °C.
•	PFASs were part of primary pyrolysis gas: purification or combustion is necessary.
•	Contamination by PFASs and their congeners could be monitored with organic fluorine.

Keywords

Sewage sludge / PFAS / Pyrolysis / Carbonization / Sludge-char / Organic fluorine

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Funding

Ministerstvo Zemědělství(QK21020022); Akademie Věd ?eské Republiky(AV 21 – Sustainable energy); Vysoká ?kola Chemicko-technologická v Praze(A1_FTOP_2024_001); Technology Agency of the Czech Republic(SS02030008)